Dehydration of acetone



Apri! 10, 1945.- R." N. sHlRAs rs'r A1. 2,373,269

I JEHYDRATION oF AcEToNn v f Filed May 26, 1942 2 Sheets-Sheet l asf April` 1-0, 1945K. R. N. fsHlRAs ET AL.

DEHYDRATION 0F AGETONE VFiled May 26, 1942 2 Sheets-Sheet 2 40o l @oo PREwz/Rfjmm ZOO lfm/enfans.' Dar/'d E Luckenb/ Patented Apr. 1o, 1945 FICE V DEHYDaA'rIoN oF aCE'roNE aussen N. shim, oakland, ana Davids. Luckenbill, Berkeley, Calif., assignors to Shell Developv ment Company, San Francisco, Calif., a corporation of Delaware Applieaaon May as, i942, serial No. 444,606

' (ci. 2oz-52) 5 Claims. This invention relates to` the preparation of tains to improvements in the dehydration of acetone byfractionaldistillation. Acetone may be produced by any one of sevl eral methods. In .most cases, regardlessof the process used for its preparation, crude acetone contains a substantial amount of water. For

' anhydrous acetone and' more particularly perexample, in the manufacture of acetone from isopropyl alcohol by catalytic oxidation or dehydrogenation of isopropyl alcohol, it is common practice to quench the gaseous mixture issuing from the reaction tube or chamber with water to separate the carbon monoxide and hydrocarbon gases produced as a result of the reaction. the acetone and unconverted alcohol together with arelatively small proportion of impurities, mostly of analdehydic character, being taken up by the quenching water.

As there are a number of uses for acetone wherein material which is substantially completely anhydrous is required y(i120 per cent water or less) it is important that a high degree of separation oi? the water present in the crude `acetone product be attained. Among the many useas a solvent for commercial coating materials, particularly nitro-cellulose, cellulose-acetate, cellulose acetobutyrate, cellulose acetopropionate, ethyl -cellulose and the like, and, in the manufacture of smokeless powder, for the gelatinization of nitro-cellulose. An anhydrous -acetone is also advantageous in the production of artificial iilaments and hypersensitive photo-v graphic films. f

In the `dehydration of aqueous acetone by fractionation, the distillation is usually carried out in a continuous manner, the aqueous acetone being continuously introduced into the distilla tion column at the desired rate, while at the same time a definite portion of theA overhead is collected as finished material, the remainder being employed as reflux.. vSince maximum column capacity is, in general, realized by operation at atmospheric pressure. or at-pressures somewhat in excess of atmospheric pressure, it has been the practice in the dehydration ofaqueous acetone by fractional distillation to operate at such pressures, However, the dehydration of acetone to less than 030% water by distillation at atmospheric or superatmospheric pressures is diiicult and uneconomical.- A high column of large diameter is required and the fuel and cooling water consumption isxcessively high, since the productlmust be distilled over. 'head at highl reflux. The operation;- moreover,

by reason of the high reflux rates necessary, is extremely time consuming, frequently requiring the devotion of a large portion of the nishing equipment of the individual plant for long periods and often constituting "bottle neck."

l It is an object ofthe present invention to provide a practical and economical method for eilecting the substantially complete dehydration of acetone by fractional distillation without the use of auxiliary water-removing materials. Another andmore particular object is to provide improvements in the dehydration of acetone by fractional distillation whereby column production capacityis increased, or which may be conversely applied to reduce column requirements. A still further object of the invention is to produce an anhydrous or substantially anhydrous acetone moreeconomically than is practically possible according to heretofore Vemployed methods `for separating water and acetone by fractional distillation.

In the separation of one 'or more components of a mixture by fractional distillation, decreased column production capacity is normally exi pected from reduction of pressure by reason of the resulting increase in vapor volum, generally necessitating a slowerl feed"rate to prevent'entrainment of liquid in vapor and consequent flooding of the column. However, it has now .beenY` found with4 respect tothe lfractionation of acetone from mixtures thereof with water that, contrary to the general rule, column capacity is not reduced but 1s materially increased by operation at pressures below atmospheric pressure, and

lfurther that for the maximum effect greatly reduced operating pressures are unnecessary,l an easily attained and maintained subatmospheric pressure in the order of 200 to 400 mm. being suillcient. According to the process of the invention, column production capacity` may, in

kmany instances, be increased 40 to 80% and the acetone product materially improved as to the Water content orfalternatively, as willbe pointed out, hereinafter with greater particularity, column capacity may bev more than doubled without increasing thevwater content of 'accompanying `drawings of which Figure I sets'v out equilibrium data obtained by the distilla- 4 a' production tion of acetone-waterA mixtures at various pressures and of which `Figure II graphically illustrates the superiority of the'present process in terms of column production capacity 4relative toy operation according to previously employed methods, the data represented covering columns of 30, 40 'and 50 equilibrium rectifying plates. l f

The presentl process for dehydrating acetone in contact with the equilibrium vapor is concen trated in acetone to the extent of 9 7 mol per cent the equilibrium vapor at 850 mm. pressure conn. jtains only 97.44 molper cent acetone, giving a volatility ratio between the two compounds of only about 41.18 at this pressure. Thus the difculties heretofore experienced in producing an l acetone of low water content by operation at pressures in excess of atmospheric pressure whereby it was thought to achieve maximum column production capacity are readily understood. Figure I further shows that when the pressure over the liquid containing 97 mol per cent acetone is 250 mm. the equilibrium vapor contains 98.7 mol percent acetone. This gives a volatility ratio between the two compounds at this` pressure of, roughly, 1%, which permits of a much higher degree of separation than is pos- `sible at 850 mm.,v and with equipment of only moderate size and heat requirements. Because ofthe increase in the relative volatility'of acetone and water resultingfrom operation at r'educed pressures, according to the process of the invention, the amount of reux necessary to attain a given product purity is much vless than the amount required to attain the same purity byoperaton at superatmospheric pressures. It is, as a matter of fact, by reducing reflux` requirements that the instant process u increases column production capacity. The amount of increase in production capacity achieved with respect to a given column depends, of course,`

upon whether or not it is also desired to increase product purity,`that is, decrease the relative amount of water present inthe finished acetone.

The practical significance of the present process in terms of its eil'ect upon column production capacity and product purity is best shown by the graph of Figure II developed from McCabe and 500 mmf pressure, at which pressure column capacity is increased only vto a slightly lesser extent, ordinary plant cooling water suiilces. Thus, assuming a forty plate nishing' column operat-f sure may be obtained in any suitable manner, for

example, by means oi a steai'n ejector or vacuum pump acting upon tlie product accumulator in communication with the condenser, allowance being made for pressure drop between these two The redux rate employed-is naturally determined by the extent of dehydration required and the number of plates in the available column as well as the exact operating pressure employed. In general, it is preferred tooperate with columns of from 20 to 60 total plates, the feed material being directed to enter upon the sixth to the fifteenth plate. For a given column, operated according to the teachings of the present invention to produce an acetone containing, for example, v0.20% water, the reux rate is, of course. much lower than if the same column should be operated at higherpressures, if it could be so operated to give a product of this Water content.

because, as has been previously stated, it is actually by reducing the amount of reiiux required that the instant process increases throughput.

The process of the invention, which has been particularly described as applied to increasing the production capacity of an acetone finishing column and/or to decrease the water content of the acetone product, may also be'applied to reduce column requirements, that is, according to the process of the invention,r columns of smaller diameter and/or containing fewer plates may be Thiele diagrams based on the experimental dataz and applying to any acetone-water mixture containing 30 to '70 'weight per cent acetone. As shownon Figure II. the reierencepointfor the capacity calculations is the column capacity at 850 mm., the heretofore most customarily employed operating pressure, with reilux sumcient to reduce the watercontent of. the acetone to 0.3'

weight per cent with the specined member of equilibrium rectiiying plates. From Figure II it is apparent that from the standpoint of production capacity the optimum operating pressure for the separation-of acetone and water is within the range 200 to -400 mm. Since the condensation temperatures of acetone at 200 and 400 mm. pressure are 21.6 C. (68 F.) and 38.3 C. (101 F.) respectively, some means of artiilcial cooling such as ammonia or sulfur dioxide may be necessary to condense the product at these pressures, but at employed'to accomplish the desired result. For example, at the heretofore customary operating pressure of 850 mm. a column of 40 to 45 total plates operated at a reflux ratio yof 5 is necessary to obtain acetone having a Water content of 0.30% while the same product purity may be achieved by the present process, and without the employment of any condensing agent other than water, with a column of not-more than 20 total plates operatedat the same reflux ratio. Furthermore. while Aa column of at least 45 to 50 plates operated at a reiiux ratio of at least 10 and at a pressure of 850 mm. is necessary to yield an acetone'product containing not more than 0.10% water, the process of the invention can Vbe advantageously operated with a column of less than 20 total plates, employing a renux ratio of only 3 to 5 and an operating pressure in the range oi from 200 to 400 mm. to obtain acetone of the same low water content (not more than about 0.1

It is to be understood that the process of the invention is broadly applicable tothe separation of water from mixtures containing acetone and water, irrespective of their source. and that the mixture distilled may or may not contain other components. The treatedmixture may predominate in acetone or it Amay predominate in water or in components other than water or acetone.

ufat'eror acetone. Excellent resultsnave been osmose Mixtures may be subjected to the process which contain as little as, for example, 1% either of.

achieved with respect to mixtures containing 50 to 539% acetone. When tile process is applied to the dehydration oi the crude acetone product ob'- tainecl by the water quenching of the reaction mixture resultizigjrom the oxidation or clichydrogenationof isopropyl alcohol, orior removal of y Water-insoluble and high boiling impurities. by suitable means is preferred. In the execution of the process, the inisliecl anhydrous acetone is ootained as'tne distillate. The residue, consisting in the main of' unconverted alcohol and water,

may loe thereoter separated int-o its components and. if desired, the alcohol may loe returned as feed to the reactor.

'lille :following example is introduced to illustrate one method of executing tlie process oi the invention. The exe-mole is not to be construed as limitative with regard to the material treated ansi the procedure employed.

` Example in aqueous acetone mixture containing acetone tially anhydrous acetone from the fractionating and Water in the weight ratioof-about 2 to l. Iwas continuously distilled in a iractionating column provided with 42 `plates. The pressure (absolute) in the column was about 300 mm. When tile reilus ratio (ratio of reflux to distillate) was l, the acetone product contained about 0.38 weight per cent water. Increasing the reflui; ratio tov 2 resulted finan acetone containing only about @.14

A weight per cent water. A still greater increase of 'the reflux ratio to 3 gave an acetone contsinin only about @,104 water. l

The same material was distilled in the same apparatus, the pressure inthe' column being maintained at about 500 mm; (absolute) Reflux ratios of 2, 3 and o resulted in an acetone distillate con taining, respectively, 0.32%, 6.18% anc. 0.09% by Weight of water.

When the same material was ydistilled. in the same apparatus, the pressure in the column' loeing Zone.

tially `anhydrous acetone from a mixture containing' acetone and water which comprises subiecting the acciones-water mixture to a fractional distillation in. a fractional-,ing acne maintained at a pressure between about 202 millimeters and loc millimeters (absolute), and separating substantially anhydrous acetone from the fractional:n

2. A process for the production of substantially anhydrous acetone irorn a mixture essentially comprising acetone and water, which mixture contains from about 1% toabout 52% by weight of Water bowl on the acetona'wliich comprises suojecting said acetonewater mixture to a :tracn ticnaloistillation in a iractionating zone maintained at a pressure of between about 200 mm.. and out) nun. (absolute). and separating sulistan zone.

3. luie process for the production of substam ytially anhydrous' acetone from a mixture containing acetone and water, the steps of introducing tlie acetone-water mixture nto'e, distillation column maintained at a temperaturesufcient to effect the vaporization .of acetone out insuillcient to .'aoorize any major1l amount of water. withdrawing substantially anhydrous acetone from the upper 'part of theoistillins' column. condensing at least'a portion of said vapors. returning atleasto part of said condensate to said column as reilux, anni maintaining said distillation column at a pressure of between about 200 mmand about eco min. (absolute), thereby increasing the relative column capacity and .the degree of dehydration as compared to the results obtained. when the distillation is selected under the same conditions out at higher pressures. l

ing atmospheric,a reflux ratio of 3 was necessaria 45 4. in' a. process for vthe production of substa tially anhydrous acetone from a mixture containing acetone and water, the steps or introducing the acetone-water mixture into an intermediate point of a distillation column maintained at a pressure of between about 2c@ mm. and about 5o@ min (absolute) and at a temperature sumclent to vsnorize the acetone, withdrawing sulostantially anhydrous acetone vapors from the upper cart of the distilling column, condensing at least late containing about 0.32% water, it was neocsf sary to employ-a. column containing 80 plates and operate with a reflux ratio of 5. .During this dis tillation the' mixture was fed to lthe twelfth plate.

We. claim as our invention: l'. A process for the production of substana portion of solo. vapors, and returning at least' a loert or solo condensate to said column as rcuux.

5. In a process for the production ol substantlally onliydrousacetone from a mixture containing acetone and' water. the steps of introducing the .acetoneWater mixtureinto an intermediate point of a distillation column maintained at .a substantial subatmospheric pressure or about 500 mm. (absolute) and at a temperature -sucicnt to veporize the acetone, withdrawing substantially anhydrous acetonevapors 'from the upper part of the distllling column, condensing at least a portion of said vapors, and returning at least a Part of said condensate to said column as reux. RUSSEL N. Smits.

DAVID B. LUCKENBHL. 

